CN1849556A - Laminated photosensitive relief printing original plate and method for producing the relief printing plate - Google Patents

Laminated photosensitive relief printing original plate and method for producing the relief printing plate Download PDF

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Publication number
CN1849556A
CN1849556A CNA2004800260501A CN200480026050A CN1849556A CN 1849556 A CN1849556 A CN 1849556A CN A2004800260501 A CNA2004800260501 A CN A2004800260501A CN 200480026050 A CN200480026050 A CN 200480026050A CN 1849556 A CN1849556 A CN 1849556A
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China
Prior art keywords
ultraviolet
layer
mask layer
radiation
mask
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CNA2004800260501A
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Chinese (zh)
Inventor
高木利哉
藤本隆史
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Eastman Kodak Co
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Tokyo Ohka Kogyo Co Ltd
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Publication of CN1849556A publication Critical patent/CN1849556A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/56—Organic absorbers, e.g. of photo-resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Abstract

A relief printing original plate including a substrate, a photosensitive resin layer thereon that is photosensitive to ultraviolet radiations, and a mask layer thereon having both ultraviolet and non-ultraviolet absorbability, the ultraviolet absorbability being deactivatable in response to receiving non-ultraviolet radiation. A method for producing a relief printing plate by using the original plate is also provided.

Description

Laminated photosensitive letterpress master and the method for making this relief printing plate
Technical field
The present invention relates to a kind of laminated photosensitive letterpress master that is used to make relief printing plate such as hectographic printing version, and a kind of method of making this relief printing plate.
Background technology
As everyone knows, hectographic printing is for using the letterpress of flexible printing plate.Because its higher printing precision, better economic efficient, multifunctionality and environment friendly, hectographic printing have obtained reappraising and are noticeable.
In Japan, more general print system is lithography and intaglio printing.Other more not general print system can comprise serigraphy.Letterpress such as hectographic printing are relatively not too general in Japan, but hectographic printing has the following advantage:
(1) hectographic printing has burr and this edition is flexible with version, and its permission is printed on the not gentle rough object as corrugated paper box.In addition, hectographic printing is quicker and more cheap than other print system.
(2) hectographic printing can be at less object, for example clear and printing cheaply on the label.
(3) compare with lithography, because can use high concentration printing ink, hectographic printing produces clearer printing.
(4) compare with intaglio printing, hectographic printing produces writings and image more clearly.
(5) because can use water color ink and complete solventless ink, UV printing ink for example, hectographic printing is eco-friendly.
(6) it is less that hectographic printing reaches stable color condition institute's time spent, therefore can reduce the ineffectivity of printed medium such as paper, thereby make hectographic printing more economically.
(7) hectographic printing needs less maintenance cost or update cost, because can only replace part version, and need not replace whole version.
(8) hectographic printing can be used for the small serial production of numerous species.
These numerous advantages are known, because letterpress is traditional ancient printing technology, and hectographic printing is a kind of of letterpress.But hectographic printing is very not general in all printing industries.
But recently, the quality of printing-ink and printing material improves, and the care of related environmental problems occurred, makes that for example letterpress of hectographic printing is reappraised.Therefore, the research and development of hectographic printing is now adding persistent erection.
State of the art about printing original edition plate is as follows:
The hectographic printing version is made by the rubber layer as composition material, thereon the engraving literal that will be printed and the negative-appearing image of figure.But, recently, photosensitive resin just be used to make the hectographic printing version (referring to for example Jap.P. disclose 2916408 and Japanese Patent Application Publication 2003-35954).Usually, this photosensitive resin comprises elasticity base-material, at least a monomer resin and light trigger.Hectographic printing master with this photosensitive resin manufacturing is a kind of board-like material, comprises base material and at least a photosensitive resin layer that forms thereon.
Use this printing original edition plate production hectographic printing version to carry out according to following method.To have corresponding to the image that will be printed, for example the film of the negative pattern of literal or figure (mask) places on the photosensitive resin layer of printing original edition plate.Then through this mask impinge actinic radiation photosensitive resin layer.With impinge actinic radiation the layer part solidify by photopolymerization.Rinse out uncured portion with developer liquids subsequently, produce development, obtain the hectographic printing version corresponding to the relief pattern of image.When carrying out hectographic printing, printing ink is applied over the upper surface of relief pattern, and the hectographic printing version is pressed on printed medium such as the paper, obtain print product.
Pointed out that the hectographic printing version of being made by photosensitive resin has the following problem that needs solution:
(i) when the negative pattern on the necessary correction mask, whole mask must be made again, because can not the part correction mask.Therefore, proofreading and correct need many step.
(ii) because negative mask is made by negative film, the shape of mask is easy to change because of the change of temperature and humidity.Therefore, even use identical mask, the precision of printing may change according to the time and the environment that carry out pattern formation step, and described pattern forms exposure and the development that step comprises photosensitive resin layer.
(iii) optical interference such as dust are easy to enter in the pattern forming process between negative mask and the photosensitive resin layer.Pattern image was inaccurate after this optical interference between mask and the photosensitive resin layer may cause exposure and development, and it may cause the printing quality of galley to degenerate.
As the countermeasure of these problems, developed so far several each tool novel structure galley (referring to for example Jap.P. disclose 2916408, Japanese Patent Application Publication 2003-35954, Japanese Patent Application Publication 2003-35955, Japanese Patent Application Publication H11-153865, Japanese Patent Application Publication H9-166875, Japanese Patent Application Publication 2001-324815 and Jap.P. disclose 2773981).The common trait of these printing original edition plates is for forming the infrared-sensitive layer at least on photosensitive resin layer.This infrared-sensitive layer can be as negative mask or positive mask.This infrared-sensitive layer is blunt for the actinic radiation that makes the photosensitive resin polymerization in the photosensitive resin layer, but has photosensitivity for infrared radiation.This infrared-sensitive is to be evaporated and/or to decompose the ability that promptly melts by being exposed to the infrared laser radiation.Therefore, the infrared-sensitive layer is also referred to as infrared ablation layer.
This infrared ablation layer of lamination can directly write down and will be printed onto image information on letterpress master such as the hectographic printing master with infrared laser, does not therefore need traditional negative or positive mask film.Printed images information corresponding to printed patterns can use a computer with the formation of numerical information form, storage, revise and output.Therefore infrared ablation layer significantly reduces the expense of Image Information Processing, and when using traditional masks film production relief printing plate, this expense is essential.
Known various composition is used for infrared ablation layer, but its basic composition is similar.For example, Jap.P. discloses 2916408 and discloses a kind of printing original edition plate with infrared ablation layer, described infrared ablation layer is by (1) at least a infrared absorbing material, (2) for the blunt material of non-infrared radiation (UV radiation), wherein infrared absorbing material and blunt material can be identical or different, and (3) at least a with photosensitive resin layer in the inconsistent substantially base-material of low molecular material make.
Stop any material of non-infrared photochemical radiation direction photosensitive resin layer transmission can be used as this blunt material.The example of suitable blunt material comprises dyestuff, dark inorganic pigments and the combination thereof that absorbs ultraviolet light or visible light.Preferred blunt material is carbon black and graphite.
Infrared absorbing material is 750 to 20, and the 000nm zone has strong absorption.The example of suitable infrared absorbing material comprises dark inorganic pigments, for example carbon black, graphite, copper chromite, chromium oxide and aluminic acid chromium-cobalt; And dyestuff, for example poly-(replacement) phthalocyanine compound, cyanine dye, squarylium cyanine dyes, chalcogen skin pyrene arylidene dyestuff.
Use traditional letterpress master, the mask layer blunt for the ultraviolet light actinic radiation melted (burn off) selectively, forms the masks area that the ultraviolet light actinic radiation can pass through.Therefore in the mask layer ablation steps that is used for obtaining the mask images layer, must provide vacuum and emptying means, in order to ablation debris is discharged outside the reactive system, to avoid ablation debris to remain in or to be attached on the photosensitive resin surface.
Even if the mask material thin layer remains in the mask images layer region that actinic radiation must pass through, then the actinic radiation amount by this mask will reduce.Therefore, mask layer melts to proceed to and exposes till the photosensitive resin layer.This ablation method causes the roughening of photosensitive resin layer exposing surface by infrared laser.It because being retained in subsequently the development step, the roughening on this exposed portions serve becomes printing-ink to be placed surface thereon, so may damage printing quality.
Summary of the invention
The present invention finishes in view of above-mentioned situation of the prior art.An object of the present invention is to provide a kind of letterpress master, it can form the mask images layer with high-contrast, but do not make the surface roughening of the photosensitive resin layer of its bottom, and provide a kind of by using this letterpress master to produce the method for relief printing plate.
In order to address the above problem, letterpress master of the present invention comprises base material; Be laminated on the described base material and be the photosensitive layer of photosensitivity for ultraviolet radiation; And be laminated to mask layer on this photosensitive layer, and described mask layer has the ability of ultraviolet radiation-absorbing and non-ultraviolet radiation, and the ultraviolet-absorbing of described mask layer is inactivation along with receiving described non-ultraviolet radiation.
The method of producing relief printing plate of the present invention comprises that with actinic radiation with the step of stamp irradiate light on the photosensitive resin layer of printing original edition plate, described printing original edition plate is by forming photosensitive resin layer production on base material; And making this edition step of developing with development liquid, the resin bed with relief pattern that is formed for printing thus on described base material obtains the described galley that is used for letterpress; Wherein the photosensitive lamination material provides with described letterpress master, described laminated material has photosensitive resin layer and the mask layer that base material and lamination one deck at least thereon have sensitivity to ultraviolet light, and described mask layer has the ability of ultraviolet radiation-absorbing and non-ultraviolet radiation, and the ultraviolet-absorbing of wherein said mask layer is inactivation along with receiving described non-ultraviolet radiation; And wherein said method further comprises: according to the step that the picture pattern that is used to print shines described mask layer with described non-ultraviolet radiation, described thus mask layer changes into and has for the transparent mask images layer that is subjected to irradiation zone of described ultraviolet radiation; The step of using described ultraviolet radiation to shine described photosensitive resin layer through described mask images layer as mask; And remove photosensitive resin layer in described ultraviolet radiation irradiation of no use and the therefore uncured unirradiated zone with described development liquid.
In the present invention with above-mentioned feature, this non-ultraviolet radiation can be infrared radiation (infrared laser) or a part of visible light.Any visible light in the not all wavelength coverage of operable visible light, but have a part of visible light of near-infrared region wavelength.Preferred light can comprise Ar laser and 1/2YAG laser.
According to above-mentioned feature, when shining mask layer according to the image that will be printed with non-ultraviolet radiation such as infrared radiation, the ultraviolet-absorbing that is subjected to irradiation zone of mask layer is with inactivation and should incite somebody to action therefore transparent for ultraviolet radiation in the zone.Therefore can form the mask images layer and not have melting of mask material.That is to say, can form the mask images layer and need not handle the optional equipment and the step of ablation debris.
If ultraviolet clear area is with melting formation by the infrared radiation in the scope of non-ultraviolet range; the so infrared irradiation zone that is subjected to can be guaranteed by the incomplete burn off of mask layer for the transparency of ultraviolet radiation; keep the certain thickness mask material in this bottom, zone; to protect the photosensitive resin laminar surface on its bottom, because the mask material on the bottom is owing to its ultraviolet-absorbing is lost in the infrared radiation that is used to melt.Remove infrared ray (non-ultraviolet ray) and be subjected to irradiation zone as follows by this melting: at first together with the advantage of this common use that makes the ultraviolet-absorbing inactivation in this zone by acid, most of infrared radiation zone can be air space, has excellent ultraviolet transparency.Secondly, the photosensitive resin laminar surface can obtain favourable protection by the not ablation layer in this bottom, zone residual mask layer.In addition, the mask film of bottom has become transparent and extremely thin for ultraviolet radiation, so its transparency for ultraviolet radiation is further improved.Therefore, by means of this common use of melting together with the ultraviolet-absorbing inactivation by infrared ray (non-ultraviolet ray) radiation, with only compare by the ultraviolet transparency that is subjected to irradiation zone that the ultraviolet-absorbing inactivation obtains by infrared radiation, infrared ray (non-ultraviolet ray) can be further improved by the ultraviolet transparency of irradiation zone, and can form mask images layer with high-contrast, and do not make the surface roughening of the photosensitive resin layer of its bottom.
These and other purpose of the present invention, feature and advantage are specifically illustrated in following detailed Description Of The Invention or are become apparent by following detailed Description Of The Invention.
Implement best mode of the present invention
As mentioned above, the present invention is characterised in that and uses the photosensitive lamination material as the letterpress master, described photosensitive lamination material has at least one deck sensitivity to ultraviolet light photosensitive resin layer and has ultraviolet-absorbing and the mask layer of non-ultraviolet-absorbing, and its ultraviolet-absorbing is inactivation along with receiving non-ultraviolet radiation such as infrared ray or Ar radiation.
In this structure, by in preset range, suitably selecting the energy of non-ultraviolet radiation such as infrared ray or Ar radiation, mask layer since the inactivation of the ultraviolet-absorbing of non-ultraviolet radiation such as infrared ray or Ar radiation can carry out not melting under the mask layer.
In addition, can adopt the energy bigger to carry out infrared radiation, make because the inactivation of the ultraviolet-absorbing of infrared radiation mask layer can carry out with melting of mask layer as non-ultraviolet radiation than above-mentioned scope.
Preferably mask layer has 1 * 10 -17To 9 * 10 -10The oxygen permeability coefficient.This exposure and the development that can suppress photosensitive resin layer by a certain amount of oxygen infiltration of mask layer to a certain extent, obtain tapered slightly pattern, it has less printing ink pattern top-surface area thereon, the print product clear picture that obtains of applying.
Preferably mask layer contains binder resin, acid forming agent and ultraviolet light absorber, and its ability that absorbs non-infrared radiation is along with contacting and inactivation with acid.
Hereinafter, with reference to the example of hectographic printing master and typographic printing master, will each element of letterpress master of the present invention be described in more detail.
(substrate layer)
The substrate layer of hectographic printing master of the present invention and typographic printing master can be for having physical property that enough printshop needs such as any base material of physical strength.The example of its material can comprise known metal, plastic sheeting, paper and compound thereof.This material can be particularly including thin polymer film, transparent foaming plastics and fabric, adhesive-bonded fabric such as glass fabric and the metal made by the polymkeric substance that produces by for example addition polymerization and linear condensation, for example steel, iron, aluminium, zinc, copper, brass and stainless steel.Preferred substrates is transparent for non-infrared radiation, makes to become possibility from back-exposure.The preferred example of base material can comprise the sheet material and the film of polyethylene terephthalate (PET), nylon, tygon, polypropylene, acrylic resin and polyester.Pet film is particularly preferred for hectographic printing.The thickness of film can be 50 to 300 μ m, is preferably 75 to 200 μ m.Can improve the thin layer coating of layer with viscosity towards the substrate surface of photosensitive resin layer.The preferred embodiment that is used for the viscosity improvement layer of hectographic printing master can comprise the potpourri of polycarbonate, phenoxy resin and polyisocyanates.The preferred embodiment that is used for the viscosity improvement layer of typographic printing master can comprise that those are recorded in the material of Japanese Patent Application Publication S61-17148, be that those contain vibrin, urethane resin, epoxy resin, acrylate resin or the ethylene-vinyl acetate resin material as principal ingredient, and those contain polyvinyl alcohol resin or the celluosic resin material as principal ingredient.
(photosensitive resin layer)
The photosensitive resin layer that is used for hectographic printing master of the present invention can be made up of elasticity base-material and photosensitive resin composition, and described photosensitive resin composition contains one or more monomers and for the polymerization initiator of non-infrared radiation sensitivity.Any photosensitive resin composition of common hectographic printing that is applicable to can use.The elasticity base-material can be made up of homopolymer, multipolymer or its potpourri, and has elastic performance.The elasticity base-material can dissolving in water-based or organic solvent, swelling or dispersion, makes this elasticity base-material to remove by washing.The examples of resins that is used for the elasticity base-material can comprise polybutadiene, polyisoprene, polydiene, the multipolymer of aromatic vinyl compound and diolefin or segmented copolymer, styrene/butadiene copolymers, the styrene/isoprene multipolymer, diolefin/acrylonitrile copolymer, ethylene/propene copolymer, the ethylene/propylene/diene hydrocarbon copolymer, ethylene/acrylic acid copolymer, diolefin/acrylic copolymer, diolefin/acrylate/acrylic copolymer, ethene/(methyl) acrylic acid/(methyl) acrylate copolymer, polyamide, polyvinyl alcohol (PVA), the graft copolymer of polyvinyl alcohol (PVA) and polyglycol, ampholyte copolymer, cellulose derivative such as alkylcellulose, hydroxy alkyl cellulose and NC Nitroncellulose, ethylene, cellulose acetate butyrate, poly-butyraldehyde, thermoprene, styrene/acrylic acid co-polymer, polyvinyl pyrrolidone and polyvinyl pyrrolidone/vinyl acetate copolymer.These polymkeric substance can use separately or use with two or more blend.The example of this base-material also can be included in solvable or dispersible binder resin in the water developer solution, and it is recorded in US Patent specification 3,458, and 311,4,442,302,4,361,640,3,794,494,4,177,074,4,431,723 and 4,517,279, and solvable in organic developer, swellable or dispersible binder resin, it is recorded in US Patent specification 4,323, and 636,4,430,417 and 4,045,231.
One or more monomers that are included in the photosensitive resin layer that is used for this hectographic printing master must be compatible with above-mentioned base-material, so that form not muddy transparent photosensitive resin layer.The example of this monomer can be for constituting the monomer of above-mentioned base-material, and be recorded in US Patent specification 4,323, the monomer in 636,4,753,865,4,726,877 and 4,894,315.
The photosensitive resin layer that is used for the typographic printing master can contain flexible base-material and photosensitive resin composition, and described photosensitive resin composition contains one or more monomers and for the polymerization initiator of non-infrared radiation sensitivity.Any photosensitive resin composition of common typographic printing that is applicable to can use.
The example of elasticity base-material can comprise partly-hydrolysed vinylite and derivant thereof, the multipolymer of acrylate and maleic acid, alkyd resin, polyethylene oxide, water-soluble or pure soluble polyamide, vinyl-vinyl acetate copolymer, polystyrene resin, phenolics, vibrin, epoxy resin and polyvinyl butyral resin, for example those are recorded in Japanese Patent Application Publication H4-240644, S61-17148, S62-187848, S63-8735, S63-10150, H1-274132, H1-287671, H2-39048, material among the open S53-2082 of H2-73810 and H4-240855 and Jap.P..Particularly preferably be the multipolymer for preparing by as the monomer of the vinyl alcohol of saponification partially or completely and another kind of monomer, described another kind of monomer is selected from (methyl) acrylic acid, (methyl) acrylamide, N-methylol (methyl) acrylamide, styrene, propylene, maleic anhydride, (methyl) vinyl cyanide and (methyl) acrylate; Etherification product by any above-mentioned multipolymer and rudimentary hydroxyalkyl (methyl) acrylamide such as methylol (methyl) acrylamide and hydroxyethyl (methyl) acrylamide prepared in reaction; By diamines such as N, N '-two (amino methyl)-piperazine and N, N '-two (beta-aminoethyl)-piperazine, dicarboxylic acid such as N, N '-two (ethyloic)-piperazine and N, the water soluble polyamide of the polymerization preparation of N '-two (ethyloic)-methyl piperazine and lower alkyl esters thereof or etheride and omega-amino acid such as N-(amino-ethyl)-N '-(ethyloic)-piperazine; And polyamide with sulfonate radical or base.
The monomer that is included in the photosensitive resin layer that is used for this typographic printing master can be one or more those materials with at least one photopolymerization alkenyl, for example (methyl) acrylic acid, (methyl) acrylate, (methyl) acrylamide, (methyl) vinyl cyanide, styrene (methyl) glycidyl acrylate, (methyl) allyl acrylate, trimethylolpropane tris (methyl) acrylate, allyl compound, vinyl ether compound and vinyl esters compound.Its preferred embodiment can comprise the condensation product of urea, thiocarbamide or its low alkyl group, rudimentary hydroxyalkyl or low alkyl group-rudimentary hydroxyalkyl derivant and the condensation of rudimentary hydroxyalkyl (methyl) acrylamide; And the polyethylene glycol di that obtains by the reaction of its hydroxyl and (methyl) acrylic acid.
The amount of monomer can be preferably 5 to 30 weight portions, and 10 to 20 weight portions more preferably are based on the base-material of per 100 weight portion photosensitive resin layers.When content of monomer was lower than above-mentioned scope, the layer that obtains after non-infrared radiation and the curing may have low abrasion resistance and chemical resistance unfriendly.When content was higher than above-mentioned scope, the photosensitive resin layer that obtains may have the low elasticity performance, therefore was unfavorable for as the hectographic printing version.
The example of polymerization initiator can comprise aromatic ketone, for example benzophenone; Benzoin ether, for example benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, alpha-hydroxymethyl benzoin methylether, α-methoxyl benzoin methylether, 2,2-diethoxy phenyl acetophenone methoxyphenyl acetophenone (2,2-dimethoxy-1,2-diphenyl second-1-ketone) and 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone; Replace or unsubstituted many ring quinones; And disclosed polymerization initiator in the United States Patent (USP) 4,460,675 and 4,894,315.This polymerization initiator can use separately or being used in combination with two or more.
The amount of polymerization initiator is 0.001% to 10% of a photosensitive resin layer general assembly (TW) in the preferred photosensitive resin layer.
The photosensitive resin composition that is used to form photosensitive resin layer can be chosen wantonly and contain adjuvant such as sensitizer, thermal polymerization inhibitor, plastifier and colorant, and it depends on required performance.The various methods that are used to prepare the photosensitive resin compound are arranged.For example, the composition that comprise can be dissolved in suitable solvent, for example forms solution in chloroform, zellon, MEK and the toluene, and can pour solution into mould, and then evaporating solvent forms plate thus.In addition, this composition can be mediated in without any the kneader of solvent or on roller mill, and can use suitable make-up machine, and for example extruder, injection machine or block press are the plate shape of desired thickness with mixture forming.
(mask layer)
Be preferred for that mask layer of the present invention comprises binder resin, acid forming agent and along with contacting and the ultraviolet light absorber of inactivation with acid.For acid forming agent is worked, mask layer can further contain photo-thermal transforming agent and the sensitizer that luminous energy is changed into heat energy.
Base-material is not particularly limited, as long as it has film forming ability and is transparent substantially for ultraviolet radiation.Preferred binder resin and photosensitive resin layer is incompatible or incompatible substantially.Especially, the binder resin that contains hydroxyl or carboxyl is preferred.The example of this binder resin can comprise polyvinyl butyral, polyvinyl acetal, epoxy resin, cellulose derivative, polyalkylene oxide derivative, urethane derivative and terpene resin.
The example of cellulose derivative can comprise methylcellulose, ethyl cellulose, hydroxylated cellulose, hydroxypropyl cellulose, cellulose ethanoate, acetyl cellulose propionate, cellulose acetobutyrateate and NC Nitroncellulose.
The example of polyalkylene oxide derivative can comprise the compound by following formula (1) to (8) expression:
Figure A20048002605000121
The example of urethane derivative can comprise the compound by following formula (9) expression:
Formula (1) arrives in (9), R 1, R 4And R 5Be hydrogen atom or alkyl, R 17, R 35Be C mH 2m(wherein m is 1 or bigger integer, and H can be substituted), R 2, R 3, R 6To R 16, R 24, R 33, R 34, R 36, R 37, R 38And R 39Be C pH 2p(wherein p is 3 or bigger integer, and H can be substituted), and n 1To n 18Be 1 or bigger integer.
When being configured for the base-material of photosensitive resin layer of the present invention with various above-mentioned base material, this base material can be used separately or use with two or more blend.
The photo-thermal transforming agent is not particularly limited, as long as it can be converted into heat energy with luminous energy.Various pigment, dyestuff, colorant and composition thereof can suitably be selected for use and make this reagent.The example of photo-thermal transforming agent can comprise many (replacement) phthalocyanine compound, cyanine dye, squarylium cyanine dyes, chalcogen skin pyrene arylidene dyestuff, two (chalcogen skin pyrenyl) polymethin dyes, oxygen base indolizine dyestuff, two (aminoaryl) polymethin dyes, merocyanine dyes, can kowtow  dyestuff, metal mercaptide salt dyestuff and oxyketone dye.In addition, also can use " Koukinousei Shikisoto Sono Ouyou (the Highlyfunctional pigments and the application) " that be disclosed in " Shikizai KougakuHandbook (the Handbook of color material engineering) " that write and publish by Asakura Shoten by Japan Society of ColorMaterial, publish by K.K.Kagaku Kogyosha, Chemical Industry supplement 30-20, the known color pigment among the open H11-277927 of 51-65 page or leaf or Jap.P..
The sensitizer that adds can be rhodamine compound and coumarin compound.Especially, rhodamine 6G (i.e. the perchlorinate compounds of neighbour-(6-ethylamino-3-ethylamino-2,7-dimethyl-3H-xanthene-9-yl) ethyl benzoate) can improve the susceptibility when adopting YAG-SHG laser as exposure light source.When adopting argon laser, use coumarin 6 (being 3-(2-[4-morpholinodithio base)-7-N, N-lignocaine cumarin) can improve susceptibility as exposure light source.
The amount of adjuvant can for 0.1 weight portion to 20 weight portions, or be preferably 2.5 weight portions to 10 weight portions, have the base-material of film forming ability based on per 100 weight portions.When content during, may can not get required UV-preventing ability less than 0.1 weight portion.When content during greater than 20 weight portions, the flexibility of mask layer and compatibility may reduce, and are not preferred therefore.The photo-thermal transforming agent can use separately or use with two or more blend.
As acid forming agent, can use when receiving heat or light time and decompose any known acid forming agent that generates acid.The example can comprise disclosed acid forming agent among the applicant Japanese Patent Application Publication 2001-260551 identical with the application.In the disclosure thing, disclose various acid forming agents, all can be used as acid forming agent of the present invention.The disclosure thing discloses the example of sulfonic acid  as effective acid forming agent.
As acid forming agent, also can use known acid forming agent, for example known triazine type or sulfonic acid oxime type acid forming agent usually ad lib.
The example of sulfonic acid oxime type acid forming agent can comprise α-(methyl sulphonyl oxygen base imido grpup)-phenylacetonitrile; α-(methyl sulphonyl oxygen base imido grpup)-4-methoxyphenyl acetonitrile; α-(trifluoromethyl sulfonyl oxygen base imido grpup)-phenylacetonitrile; α-(trifluoromethyl sulfonyl oxygen base imido grpup)-4-methoxyphenyl acetonitrile; α-(ethylsulfonyl oxygen base imido grpup)-4-methoxyphenyl acetonitrile; α-(sulfonyl propyl base oxygen base imido grpup)-4-methoxyphenyl acetonitrile and α-(methyl sulphonyl oxygen base imido grpup)-4-bromophenyl acetonitrile.
The example of triazine type acid forming agent can comprise triaizine compounds, for example 2, two (trichloromethyl)-6-[2-(2-furyl) vinyl of 4-]-the s-triazine, 2, two (trichloromethyl)-6-[2-(5-methyl-2-furyl) vinyl of 4-]-the s-triazine, 2, two (trichloromethyl)-6-[2-(5-ethyl-2-furyl) vinyl of 4-]-the s-triazine, 2, two (trichloromethyl)-6-[2-(5-propyl group-2-furyl) vinyl of 4-]-the s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 5-Dimethoxyphenyl) vinyl]-the s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 5-diethoxy phenyl) vinyl]-the s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 5-dipropoxy phenyl) vinyl]-the s-triazine, 2, two (trichloromethyl)-6-[2-(3-methoxyl-5-ethoxyl phenenyl) vinyl of 4-]-the s-triazine, 2, two (trichloromethyl)-6-[2-(3-methoxyl-5-propoxyl group phenyl) vinyl of 4-]-the s-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-methylenedioxyphenyl base) vinyl]-the s-triazine, 2, two (the trichloromethyl)-6-(3 of 4-, 4-methylenedioxyphenyl base)-the s-triazine, 2,4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) phenyl-s-triazine, 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) styryl phenyl-s-triazine and 2,4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) styryl phenyl-s-triazine.
In the embodiment of subsequent discussion, use CP-77 (ProductName, by Asahi DenkaCo., Ltd. make, 3-methyl-2-butynyl-hexafluoro-antimonic acid four sulfoniums) and RED-Triazine (ProductName, by Sanwa Chemical Co., Ltd. makes, 2-{2-(4-lignocaine-2-aminomethyl phenyl) vinyl }-4, two (the trichloromethyl)-s-triazines of 6-) as acid forming agent.
The amount of acid forming agent that will be involved can be 10 to 80 weight portions, is preferably 30 to 60 weight portions, has the base-material of film forming ability based on per 100 weight portions.When the content of acid forming agent is lower than 10 weight portions, be used to make the sour growing amount possibility of UV Absorption inactivation not enough.When the content of acid forming agent was higher than 80 weight portions, the flexibility of mask layer and compatibility may reduce, and were not preferred therefore.Acid forming agent can use separately or use with two or more blend.
The ultraviolet light absorber that uses as feature of the present invention can be the compound of any kind of, as long as the ability of its ultraviolet radiation-absorbing is along with contacting and inactivation with any or multiple acid, alkali and free radical.The suitable example of ultraviolet light absorber can comprise azomethine compounds.Azomethine compounds is the compound with azomethine group, and with integration compound ultraviolet radiation-absorbing.Azomethine compounds has the ability that is decomposed into aldehyde and amine when contacting with any or multiple acid, alkali and free radical.
As the optional member of mask layer, can propagate agent to wherein adding acid.Interpolation acid propagation agent can improve the exposure susceptibility in the exposure process, the photo-thermal transforming agent is converted into heat energy with the luminous energy of non-ultraviolet radiation in described exposure process, acid forming agent receives this heat energy and produces acid, and it makes the ultraviolet-absorbing inactivation of ultraviolet light absorber subsequently.
Mask layer can be dissolved in the organic solvent by the composition that will be used to form mask layer in preparation resin combination process, and the solution that obtains is applied on the photosensitive resin layer, evaporates organic solvent then and forms.The example of organic solvent can comprise ether, for example butyl oxide, isopropyl ether, two  alkane and tetrahydrofurans; Ketone, for example acetone, metacetone, MEK, methyl isobutyl ketone, methyl propyl ketone and cyclohexanone; Ester, for example ethyl acetate, n-propyl acetate and n-butyl acetate; And aromatic solvent, for example benzene, toluene and dimethylbenzene.These organic solvents can use separately or use with two or more potpourri.
Hectographic printing master of the present invention and typographic printing master can be chosen wantonly, and the protective seam that is used to protect mask layer that provides on mask layer is provided.The cover layer that provides on the mask layer surface also can be provided this layer.Can on this cover layer, provide protective seam.
Protective seam can be for being used for any known protective seam of common hectographic printing, for example sheet metal, plastic sheeting, the scraps of paper and compound thereof.The example can be particularly including thin polymer film, and for example those are by thin polymer film, transparent foaming plastics and fabric, adhesive-bonded fabric such as glass fabric and metal such as steel and aluminium of addition polymerization and linear condensation production.Film can be made by polyamide, polyester, polyolefin and Polyvinylchloride.Film can be preferably polyethylene film, mylar, polypropylene film or its laminated material.Protective seam can be preferably form of film, and its thickness can be 10 to 500 μ m, and is preferably 20 to 200 μ m.
The material of cover layer is not particularly limited, as long as it has film forming ability and for the ultraviolet radiation substantially transparent, and can be preferably incompatible with the aforementioned mask layer or incompatible substantially.Its instantiation can comprise polyvinyl acetal and polyvinyl butyral.
Can choose wantonly between protective seam and the mask layer separation layer is provided.Replacedly, as discussed abovely can provide the cover layer betwixt.By this separation layer is provided, before mask layer is exposed to stamp light, peels off protective seam and can become more convenient, and can prevent mask layer surface because this peeling off and roughening.By this cover layer is provided, when mask layer exposes, can protect this mask layer to avoid fusion.
To illustrate in greater detail the example of the method that is used to make hectographic printing master of the present invention and typographic printing master now.Prepare photosensitive resin composition by mixing elasticity base-material, monomer, polymerization initiator and other composition.This photosensitive resin composition is molded as the hot melt form, rolls to desired thickness then.Replacedly, can between base material and temporary protection layer, extrude then, roll to desired thickness then with extruder with this photosensitive resin composition fusion, mixing, the degassing and filtration.As another replacement scheme, base material and protective seam can be put into mould, then this photosensitive resin composition is injected between base material and the protective seam.As any result of these methods, photosensitive resin layer is in turn laminated on the base material.Subsequently, the resin combination (mask layer material) that will contain base-material, photo-thermal transforming agent and ultraviolet light absorber directly is applied over the photosensitive resin laminar surface and forms mask layer, wherein said base-material has film forming ability, and the ability of ultraviolet light absorber ultraviolet radiation-absorbing is along with contacting and inactivation with acid.Replacedly, resin combination (mask layer material) can be applied over protective seam and form mask layer.After mask layer is removed the temporary protection layer, or do not remove, by applying heat and/or power, mask layer is laminated on the photosensitive resin layer, described photosensitive resin layer is laminated on the base material.As the result of this process, can make the hectographic printing version.Replacedly, hectographic printing version can make by order laminated mask, photosensitive resin layer and base material on protective seam.
Use the hectographic printing master and the typographic printing master that obtain in the aforementioned production method, the hectographic printing version can be made in accordance with the following methods: use non-ultraviolet radiation, for example infrared laser or above-mentioned part visible light are corresponding to the patterned illumination mask layer that will be printed, mask layer changes the mask images layer into thus, and its raying part has become transparent.Subsequently, via the mask images layer as mask, with ultraviolet photochemical radiation irradiation photosensitive resin layer.The ultraviolet ray of removing photochemical radiation irradiation of ultraviolet ray of no use and therefore uncured photosensitive resin layer by development liquid radiation areas not form the print layout picture then.As the example of non-ultraviolet radiation, wavelength is 750nm to the infrared laser of 2000nm is preferred.The example of this infrared laser can comprise argon laser, krypton ion laser, helium-neon laser, He-Cd laser, ruby laser, glass laser, titanium-sapphire laser, dye laser, nitrogen laser, metallic vapour laser, semiconductor laser and YAG laser.Can select the optimal laser of condition.Especially, the wavelength Nd-YAG laser that to be 750nm be 1060nm to semiconductor laser and the wavelength of 880nm is preferred.The laser beam generating apparatus that generates infrared laser can make and digital image information directly can be reflexed to the hectographic printing master with drive unit by computer control.
As the example of the non-ultraviolet radiation in the visible region, what wavelength was 450nm to 700nm is only preferred.As mentioned above, its preferred examples can comprise that wavelength peak is the Ar laser of about 488nm and the wavelength peak 1/2YAG laser for about 532nm.
The ultraviolet radiation that is used to shine photosensitive resin layer among the present invention is that the wavelength ratio visible light is shorter, has the electromagnetic wave that is approximately above-mentioned infrared radiation, Ar laser and 1/2YAG optical maser wavelength.Ultraviolet radiation is preferably wavelength coverage than shorter visible light of the 488nm wavelength of above-mentioned Ar laser and the electromagnetic wave in the ultraviolet range, more preferably wavelength peak is 300 to the electromagnetic wave of 450nm, and more preferably wavelength peak is 350 to 400nm electromagnetic wave.The example of launching the light source of this ultraviolet radiation can comprise high-pressure sodium lamp, ultraviolet fluorescent lamp, carbon arc lamp and xenon lamp.The developer that is used for development treatment can be any material, as long as uncured photosensitive resin layer can dissolving, swelling or is scattered in wherein, and for example organic solvent, water and water base and half group water solution.The chemical property of the resin bed that will be removed is depended in the selection of developer liquids.The organic solvent that is suitable as developer can comprise aromatics and aliphatic hydrocarbon solvent and aromatics and aliphatic halogenated hydrocarbons solvent and any of these solvent and suitably pure potpourri.Half suitable water base developing agent can contain water or water miscibility organic solvent, and alkali compounds.Suitable water base developing agent can be water; The aqueous solution of ester such as heptyl acetate and acetate 3-methoxyl butyl ester for example; Hydrocarbon, for example aqueous solution of petroleum fraction, toluene and naphthalane; Chlorinated solvent, for example aqueous solution of zellon; Amine, for example aqueous solution of monoethanolamine, diethanolamine and triethanolamine; And the aqueous solution of NaOH, potassium hydroxide, sodium carbonate or ammoniacal liquor.These developer liquids can be chosen wantonly with alcohol and mix as propyl alcohol, butanols and amylalcohol.Cleaning treatment can be carried out in many ways, comprises the immersion developer liquids, scrubs from nozzle ejection liquid and with brush.
When preparation hectographic printing version, hectographic printing master or typographic printing master can be attached to rotatingcylindrical drum, and use non-ultraviolet radiation subsequently, with the ultraviolet radiation irradiation, carry out development treatment then, then with the further productive capacity of improving galley.
Embodiment
Illustrate in greater detail the present invention by the following examples.But following examples only are used to illustrate preferred embodiment.Therefore, should understand and to think that the present invention is limited to these embodiment.Among the embodiment, optical density (OD) is measured by spectrophotometer (model U-2000 is made by HitachiLtd.).
Embodiment 1
To be dissolved in cyclohexanone as the hydroxypropyl cellulose (by Nippon Soda Co., the Ltd. preparation) of base-material and obtain uniform 10wt% base-material solution.50 these base-material solution of gram are mixed with the 0.5g acid forming agent, and described acid forming agent (ProductName: CP-77, by Asahi Denka Co., Ltd. preparation, 3-methyl-2-butynyl-hexafluoro-antimonic acid four sulfoniums) generation acid when reception is hot.Stir the mixture and make it even.Further with potpourri and 0.75g ultraviolet light absorber and 0.25g photo-thermal transforming agent (ProductName: NK-4432, by Nihon Kanko Shikiso K.K. preparation) mix, prepare even mask material solution, described ultraviolet light absorber (ProductName: Shigenox CV-2 is prepared by Hakkol Chemical K.K.) has the ability of losing ultraviolet-absorbing along with contact acid.
Mask material solution is applied over the PET film (protective seam (D)) with 100 μ m thickness, and has the mask layer (C) of 5 μ m to 8 μ m dry thickness in the formation in 5 minutes of 80 ℃ of dryings.When measuring with spectrophotometer (model U-2000, by Hitachi Ltd. make), mask layer (C) is that the optical density (OD) of the light (ultraviolet radiation) of 370nm is 2.5 for wavelength.Therefore, determine that this mask layer is blunt for ultraviolet radiation.
By being 240 with 100 weight portion mean molecular weight, 000 styrene/butadiene copolymers (ProductName: model D-1155, by JSR Shell Elastomer Co., Ltd. preparation), 70 weight portion mean molecular weight are 1,000 liquid poly-(1, the 2-butadiene) (ProductName: Nisso PB-1000, by Nippon Soda Co., Ltd. preparation), 10 weight portion trimethylolpropane triacrylates, 3 weight portion methoxyphenyl acetophenones, 0.05 weight portion 2,6-two-tertiary butyl-4-hydroxy toluene and 0.002 weight portion dyestuff (ProductName: Oil Blue #503, by Orient ChemicalIndustries, Ltd. preparation) being dissolved in 0.2 weight portion tetrahydrofuran prepares photosensitive resin composition.By using high-viscosity pump, this photosensitive resin composition is upward formed thin slice with 1.7mm thickness at the base material that is made of the polyethylene terephthalate sheet material (A) via the extruder extrusion molding.This method forms photosensitive resin layer (B).
Subsequently; bond roll carries out lamination with exerting pressure; make photosensitive resin layer (B) towards and adhere to mask layer (C), obtain the photosensitive compound of multilayer (hectographic printing master), wherein base material (A)-photosensitive resin layer (B)-mask layer (C)-and protective seam (D) with this order lamination and integrated.
Remove protective seam (D) afterwards from the hectographic printing master that obtains; the mask layer (C) that exposes with infrared ray (non-ultraviolet ray) laser beam irradiation of stamp; the infrared laser beam of described stamp is output as the semiconductor laser of 600mW from energy; wavelength is 830nm; mask pattern resolution is 100 lines per millimeters, and energy density is 3J/cm 2Though the energy density 3J/cm of semiconductor laser 2Can not cause melting of mask layer (C), but this energy is enough to make the photo-thermal transforming agent in the mask layer (C) to excite generation heat.
In the mask layer that had shone with infrared laser beam (C) zone, as discussed above can not melt, but the luminous energy exciting light thermal transition agent that so applies makes the photo-thermal transforming agent produce heat energy.This heat energy excites the acid forming agent in those zones, makes this acid forming agent produce acid, the ultraviolet-absorbing inactivation of ultraviolet light absorber thus at area of irradiation.Therefore the mask layer (C) that carries out stamp irradiation with infrared laser has by the zone of losing ultraviolet-absorbing and other stamp sub-image that still keeps the zone of ultraviolet-absorbing to form.Ultraviolet-absorbing has been lost in the zone of shining with infrared laser therefore, and can pass through immediately to its ultraviolet radiation that applies.On the contrary, the zone of infrared laser of no use irradiation keeps original ultraviolet-absorbing, and is absorbed and can not passes through this zone to the ultraviolet radiation that it applies.
Use the patterning irradiation of the mask layer (C) of infrared laser therefore to produce to have by mask images layer (C ') for the potential pattern image that transparency limited of ultraviolet radiation.This mask images layer (C ') is gone up the pattern that forms can be the image of literal or figure usually.In the present embodiment, form character pattern.Measure zone with spectrophotometer (ProductName: U-2000, by Hitachi Ltd. make), promptly lost in the zone of ultraviolet-absorbing mask images layer (C ') for the optical density (OD) of 370nm wavelength light with the infrared laser irradiation.The optical density (OD) of measuring is 0.3, determines that thus ultraviolet radiation is easy to therefrom penetrate.
Making this laminated composites stand centre wavelength then is that 370nm, energy density are 75mJ/cm 2The back-exposure that carries out from substrate layer (A) side of ultraviolet radiation.Subsequently, from the side of mask images layer (C ') with 2500mJ/cm 2Energy density carry out main exposure via mask images layer (C ').
As the result of main ultraviolet exposure, photosensitive resin layer (B) shines with ultraviolet ray according to the sub-image pattern in the mask images layer (C ').In the zone with the ultraviolet ray irradiation, cross-linking reaction and curing take place.Remove mask images layer (C ') and photosensitive resin layer (B) in uncrosslinked zone at 25 ℃ by four minutes development treatment with aromatic hydrocarbyl developer (ProductName: FDO-S2, by Tokyo Ohka KogyoCo., Ltd. preparation).As a result, go up the relief image that formation is made up of cured resin at substrate layer (A), wherein photosensitive resin solidifies in the structure of required character image.
On the print surface that obtains, the do not develop adhesion again of chip or other material.After the development treatment, by heating 50 minutes dry these plates at 55 ℃.Subsequently, be that the Ultraluminescence of 250nm is carried out aftertreatment to this plate with centre wavelength, and further post-exposure is that 370nm, energy density are 3000mJ/cm in centre wavelength 2Ultraviolet radiation, to obtain the hectographic printing version.
Print on art paper with the hectographic printing version that makes thus.The result produces the print product with clear character image.
Embodiment 2
By being 240 with 100 weight portion mean molecular weight, 000 styrene/butadiene copolymers (ProductName: model D-1155, by JSR Shell Elastomer Co., Ltd. preparation), 70 weight portion mean molecular weight are 1,000 liquid poly-(1, the 2-butadiene) (ProductName: Nisso PB-1000, by Nippon Soda Co., Ltd. preparation), 10 weight portion trimethylolpropane triacrylates, 3 weight portions 2,2-dimethoxy-1,2-diphenyl second-1-ketone (having another name called benzyl methyl ketal), 0.05 weight portion 2,6-di-t-butyl-4-hydroxy-methylbenzene and 0.002 weight portion dyestuff (ProductName: Oil Blue #503, by Orient Chemical Industries, Ltd. preparation) being dissolved in 0.2 weight portion tetrahydrofuran prepares photosensitive resin composition.By using high-viscosity pump via the extruder extrusion molding, upward forming sheet material is used to form photosensitive resin layer (B) at the base material that is made of the polyethylene terephthalate sheet material (A) with 1.7mm thickness with this photosensitive resin composition.With the method production hectographic printing master identical, except forming photosensitive resin layer (B) with preceding method with embodiment 1.The infrared laser that use is used to form mask images layer (C ') makes the hectographic printing master experience stamp irradiation that obtains thus, use ultraviolet radiation via mask images layer (C ') irradiation photosensitive layer (B), and use the method identical to carry out development treatment subsequently, obtain thus forming on it and have the hectographic printing version of character image with embodiment 1.Use the hectographic printing version obtain thus, use the method identical to print with embodiment 1.The print product that obtains has the character image more clearly than embodiment 1.
Embodiment 3
Prepare the hectographic printing master with the method identical with embodiment 1, except when during preparation mask layer (C), deacidification generates outside the agent, agent (ProductName: Acpress 3, by Tokyo Zairyo Co., Ltd. makes) is propagated in additional mixing 0.5g acid.The infrared laser that use is used to form mask images layer (C ') makes the hectographic printing master experience stamp irradiation that obtains thus, use ultraviolet radiation via mask images layer (C ') irradiation photosensitive layer (B), and use the method identical to carry out development treatment subsequently, obtain thus forming on it and have the hectographic printing version of character image with embodiment 1.Use the hectographic printing version obtain thus, use the method identical to print with embodiment 1.The print product that obtains has the character image more clearly than embodiment 1.
Embodiment 4
Prepare the hectographic printing master with the method identical with embodiment 3.Use from the stamp light of infrared ray (non-ultraviolet ray) laser beam with character pattern irradiation hectographic printing master, described infrared laser beam is output as the semiconductor laser of 600mW from energy, and wavelength is 830nm, and resolution is 100 lines per millimeters, and energy density is 4J/cm 2This energy density 4J/cm 2Be enough to that mask layer (C) is melted and excite the photo-thermal transforming agent in the mask layer (C) to generate heat.
The selectivity of finishing mask layer (C) before the full depth of this mask layer melts melts.As a result, a part of mask layer of residual about 1 μ m in the zone of having shone with infrared laser beam.In this residual mask layer, hot by generating with the infrared laser beam irradiation, and pass through the hot acid that generates.Ultraviolet-absorbing wherein is because acid and inactivation.
Melt with certain depth in the zone of shining with infrared laser, makes the major part of this layer be removed and so and inactivation.In addition, wherein residual part becomes ultraviolet radiation transparent.Therefore, become than mask layer inactivation wherein by irradiation zone but the mask layer among the embodiment 1 and 2 that does not melt be subjected to irradiation zone more transparent.
In with the infrared laser irradiation and the zone of melting, the residual fraction of the mask layer of form of film prevents that the surface of the photosensitive resin layer of bottom (B) is because high power infrared laser bundle and roughening.As a result, can obtain having the relief pattern of flat top.
, shine photosensitive resin layer and use the method identical to carry out development treatment as mask with this mask images layer (C ') that obtains, obtain the hectographic printing version thus with ultraviolet radiation with embodiment 1 and 2.
With the hectographic printing version that obtains thus, use the method identical to print with embodiment 1 and 2.The print product that obtains has the character image more clearly than embodiment 2.
Because ablation process is carried out in handling the process of mask layer (C) with production mask image layer (C ') in the present embodiment, thus vacuum and exhaust apparatus provided so that remove and melt fragment, if it is present on the mask images layer (C ').
Embodiment 5
Prepare the hectographic printing version with the method identical with embodiment 1, except using polyvinyl alcohol (PVA) (ProductName: PVA 4170, by Kuraray Co., Ltd. preparation) as base-material, and the CP-77 of use 2.5g (by Asahi Denka Co., the Ltd. preparation, 3-methyl-2-butynyl-hexafluoro-antimonic acid four sulfoniums) as acid forming agent, and the TX-EX-807K of use 0.25g (by NihonShokubai Co., the Ltd. preparation) is as the photo-thermal transforming agent, with preparation mask layer (C).
Print with the hectographic printing version that makes thus.The result produces the print product with clear character image.
Embodiment 6
To be dissolved among pure water/IPA=2/1 as the polyvinyl alcohol (PVA) (ProductName: PVA 405, by Kuraray Co., Ltd. prepares) of base-material, obtain uniform 10wt% solution.This solution of 50g and 0.5g acid forming agent (ProductName: SIS-001, by Sanwa Chemical Co., Ltd. prepares) are mixed.Stir the mixture and make it even.Further with potpourri and 1.5g ultraviolet light absorber and 1.0g photo-thermal transforming agent (ProductName: S 0306, by Nihon Sieber Hegner K.K. preparation) mix, the preparation homogeneous solution, described ultraviolet light absorber (ProductName: ShigenoxCV-2W is by Hakkol Chemical K.K. preparation) has the ability of losing the UVA district along with contact acid.
With the solution of preparation thus be applied over have 100 μ m thickness the PET film as protective seam (D), and form 80 ℃ of dryings 5 minutes and to have the ultraviolet screener layer (C) of 3 μ m to 6 μ m dry thickness.This layer allows the only zone by having shone with non-ultraviolet ray of ultraviolet radiation.Find that mask layer (C) is 2.5 in the optical density (OD) of 370nm wavelength.
100 weight portion saponification are dissolved in the 200 weight portion hot water than the partly-hydrolysed PVA, 100 weight portion photosensitized reaction products, 10 weight portion ethylene glycol, 4 weight portion benzoin iso-propylethers and the 0.05 weight portion methylnaphthohydroquinone that for 73mol% and the degree of polymerization are 500 obtain solution.This solution is distributed on the mylar with the preformed dizzy layer that disappears, and 40 ℃ of dryings 15 hours, forming thickness was the photosensitive layer of 0.7mm.
The photosensitized reaction product of above-mentioned use is with following method production: 0.25 weight portion methylnaphthohydroquinone is dissolved in 10 weight parts waters, to wherein adding 74 weight portion diformazan alcohol ethers, 202 weight portion N hydroxymethyl acrylamides and 2 weight portion ammonium chlorides in addition.80 ℃ the heating and stirred this potpourri 2 hours.Then the reaction product that obtains is poured in the 1000 weight portion acetone.Obtain condensation polymerization (photosensitized reaction product) by the filtered and recycled sediment.
With water: the mixed solvent of methyl alcohol=1: 2 (weight ratio) is applied over the photosensitive layer surface that forms with said method, forms extremely thin solvent layer.With the protective seam (D) of cambium layer (C) is laminated thereon on it, make layer (C) contact with photosurface, suppress this laminated material then, be used for the photosensitive resin plate of typographic printing with production.
The protective seam (D) of peeling off the photosensitive resin plate that obtains finds that layer (C) shifts and adhere to the photosensitive layer surface afterwards.Then with infrared laser beam irradiation layer (C) with distillation (melting) layer (C) optionally, described infrared laser beam is output as the semiconductor laser of 600mW from energy, wavelength is 830nm, the resolution line is 100 lines per millimeters, irradiation energy is 3J/cm 2The optical density (OD) of measuring the distillation zone of finding layer (C) is 0.2.Subsequently, carry out 1440mJ/cm in the ultraviolet radiation of 370nm via selectivity sublimation layer (C) with centre wavelength 2Main exposure.Print surface was developed 2 minutes in 35 ℃ of hot water with brush type cleaning machine.On the print surface that obtains, the do not develop adhesion again of chip or other material.Dry then this plate and with centre wavelength in the ultraviolet radiation of 370nm with 1000mJ/cm 2Carry out post-exposure, obtain the typographic printing version.Print with this typographic printing version.The result produces the print product with clear character image.
Embodiment 7
As the base-material of the mask material solution that is used for mask layer (C), hydroxypropyl cellulose (by Nippon Soda Co., the Ltd. preparation) is dissolved in cyclohexanone obtains uniform 10wt% base-material solution.This base-material solution of 50g and 0.5g acid forming agent (ProductName: RED-Triazine, by SanwaChemical Co., Ltd. prepares) are mixed, and stirring makes it even.Further potpourri and 0.75g ultraviolet light absorber and 0.25g sensitizer (7-lignocaine-3-(2-benzimidazolyl) cumarin) are mixed with even mask material solution, described ultraviolet light absorber (ProductName: Shigenox CV-2 is prepared by Hakkol Chemical K.K.) has the ability of losing ultraviolet-absorbing along with contact acid.With the method production hectographic printing master identical, except using aforementioned solution as mask material solution with embodiment 1.
Remove protective seam (D) afterwards from the hectographic printing master that obtains, with the mask layer (C) that Ar laser beam (non-ultraviolet ray) irradiation is exposed, the mask pattern resolution of described Ar laser beam is 100 lines per millimeters, and energy density is 1J/cm 2This energy density 1J/cm 2Be enough to excite the photo-thermal transforming agent in the mask layer (C) to generate heat.
Use the stamp irradiation of the mask layer (C) of Ar laser therefore to produce to have by mask images layer (C ') for the potential pattern image that transparency limited of ultraviolet radiation.This mask images layer (C ') is gone up the pattern that forms can be the image of literal or figure usually.In the present embodiment, form character pattern.Measure the zone with the Ar laser radiation with spectrophotometer (ProductName: U-2000 is made by Hitachi Ltd.), promptly lost in the zone of ultraviolet-absorbing, mask images layer (C ') is for the optical density (OD) of 370nm wavelength light.The optical density (OD) of measuring is 0.3, determines that thus ultraviolet radiation is easy to therefrom penetrate.
Making this plate stand centre wavelength then is that 370nm, energy density are 75mJ/cm 2The back-exposure that carries out from substrate layer (A) side of ultraviolet radiation.Subsequently, from the side of mask images layer (C ') with 2500mJ/cm 2Energy density carry out main exposure.
As the result of main exposure, photosensitive resin layer (B) is exposed to ultraviolet radiation according to the sub-image pattern in the mask images layer (C '), and in the zone of ultraviolet radiation irradiation cross-linking reaction and curing takes place.Remove mask images layer (C ') and photosensitive resin layer (B) in uncrosslinked zone at 25 ℃ by four minutes development treatment with aromatic hydrocarbyl developer (ProductName: FDO-S2, by Tokyo Ohka KogyoCo., Ltd. preparation).As a result, go up the relief image that formation is made up of cured resin at substrate layer (A), wherein photosensitive resin solidifies in the structure of required character image.
On the print surface that obtains, the do not develop adhesion again of chip or other material.After the development treatment, by heating 50 minutes dry these plates at 55 ℃.Subsequently, be that the Ultraluminescence of 250nm is carried out aftertreatment to this plate with centre wavelength, and further post-exposure is that 370nm, energy density are the ultraviolet radiation of 3000mJ/cm2 in centre wavelength, to obtain the hectographic printing version.
Print on art paper with the hectographic printing version that makes thus.The result produces the print product with clear character image.
The oxygen permeability coefficient that is used as the polyvinyl alcohol resin of the base-material in the present embodiment is 9.64 * 10 -13The oxygen permeability coefficient that is used for the hydroxypropyl cellulose of embodiment 1 is 4.11 * 10 -11Therefore, the oxygen perviousness of the mask layer of embodiment 5 (C) is lower than the oxygen perviousness of the mask layer (C) of embodiment 1.In other words, the mask layer of embodiment 1 (C) has higher oxygen perviousness, and when photosensitive resin layer exposed, it may cause the amount of the oxygen that exists on the photosensitive resin laminar surface higher.The existence of this oxygen causes the cone shaped pattern outline, and small-sized pattern top is as the point that is used to print after exposure and development.Has a sharpness that helps to improve print product than the print surface (will apply printing ink) at the pattern top of small size this to it.The detailed contrast of the print product that obtains among embodiment 1 and the embodiment 5 shows obtain the more print product of high definition in embodiment 1.This developing pattern characteristic can be passed through 1 * 10 -12To 9 * 10 -10Scope in regulate mask layer (C) oxygen permeability coefficient obtain.
Embodiment 8
Prepare mask material solution with the method identical with embodiment 1.
To contain 5% polyvinyl butyral (ProductName: S-LEC KW-3; by SekisuiChemical Co.; Ltd. aqueous solution preparation) is applied over the PET film that thickness is 100 μ m (protective seam (D)), and 100 ℃ of dryings 3 minutes, forming so-called dry thickness was the cover layer (E) of 3 μ m.The above mask material solution that obtains is applied over cover layer (E) surface, and 80 ℃ of dryings 5 minutes, forming dry thickness was the mask layer (C) of 5 to 8 μ m.
With the method identical, go up at the substrate layer that constitutes by the polyethylene terephthalate sheet material (A) and to form photosensitive resin layer (B) with embodiment 1.Subsequently; carry out lamination with pressure roller; make photosensitive resin layer (B) adhere to mask layer (C), obtain the photosensitive compound of multilayer (hectographic printing master), wherein base material (A)-photosensitive resin layer (B)-mask layer (C)-cover layer (E)-and protective seam (D) with this lamination and integrated in proper order.
Remove protective seam (D) afterwards from the hectographic printing master that obtains; infrared ray (non-ultraviolet ray) laser beam with stamp is shone mask layer (C) via the cover layer (E) that exposes; the infrared laser beam of described stamp is output as the semiconductor laser of 600mW from energy; wavelength is 830nm; mask pattern resolution is 100 lines per millimeters, and energy density is 3J/cm 2As described in embodiment 1, the energy density 3J/cm of semiconductor laser 2Can not cause melting of mask layer (C), but this energy is enough to make the photo-thermal transforming agent in the mask layer (C) to excite generation heat.By receiving the irradiation of stamp infrared laser, mask layer (C) becomes the mask images layer (C ') with the sub-image that is limited by the transparency for ultraviolet radiation.
Making photosensitive resin layer (B) back-exposure from the side of substrate layer (A) then is that 370nm, energy density are 75mJ/cm in centre wavelength 2Ultraviolet radiation.Subsequently, this photosensitive layer (B) via mask images layer (C ') and cover layer (E) from mask images layer (C ') side with 2500mJ/cm 2Energy density carry out main exposure.
As the result of main exposure, photosensitive resin layer (B) is exposed to ultraviolet radiation according to the sub-image pattern in the mask images layer (C ').In the zone with the ultraviolet radiation irradiation, cross-linking reaction and curing take place.Remove cover layer and mask images layer (C ') and photosensitive resin layer (B) in uncrosslinked zone at 25 ℃ by four minutes development treatment with aromatic hydrocarbyl developer (ProductName: FDO-S2, by Tokyo Ohka KogyoCo., Ltd. preparation).As a result, go up the relief image that formation is made up of cured resin at substrate layer (A), wherein this photosensitive resin solidifies in the structure of required character image.
On the print surface that obtains, the do not develop adhesion again of chip or other material.After the development treatment, by heating 50 minutes dry these plates at 55 ℃.Subsequently, be that the Ultraluminescence of 250nm is carried out aftertreatment to this plate with centre wavelength, and further post-exposure is that 370nm, energy density are 3000mJ/cm in centre wavelength 2Ultraviolet radiation, to obtain the hectographic printing version.
Print on art paper with the hectographic printing version that makes thus.The result produces the print product with clear character image.
Embodiment 9 to 20
Below the embodiment 9 to 20 that discusses be characterised in that use the part of NC Nitroncellulose (cellulose derivative) as contained base-material in the photosensitive resin layer.
NC Nitroncellulose (by Asahi Kasei Corporation preparation) is dissolved in cyclohexanone obtains uniform 10wt% solution.Further any of the base material of record in this solution of 50g and the 6.25g following table 1 mixed, and be stirred to evenly.Further this potpourri and 0.5g acid forming agent (ProductName: CP-66, by Asahi Denka Co., Ltd. prepares) are mixed, and be stirred to evenly.Further with this potpourri and 1.50g ultraviolet light absorber and 0.25g photo-thermal transforming agent (ProductName: NK-4432, by Nihon Kanko Shikiso Co., Ltd. preparation) mix, the preparation homogeneous solution, described ultraviolet light absorber (ProductName: Shigenox CV-2 is prepared by Hakkol Chemical K.K.) has the ability of losing the UVA district along with contact acid.
The galley that is used for hectographic printing with the formulations prepared from solutions of the embodiment 9 to 20 for preparing more than each.Use these galley printings to produce character image more clearly than embodiment 1.
Table 1
Embodiment Base-material (ProductName or chemical formula) Manufacturer
9 Adeka polyether P-400 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
10 Adeka polyether BPX-11 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
11 Adeka polyether EDP-450 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
12 Adeka Carpol M-110 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
13 Adeka Carpol DL-80 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
14 Adeka Carpol GL-100 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
15 YS Polystar U Yasuhara Chemical Co.，Ltd. Terpene phenolic resin
16 HO{(CH 2)nO} 10H n＝6 - Poly propylene oxide derivative
17 HO(ROCONH) 4ROH R＝(CH 2)m m＝6 - Poly-alkyl polyurethane
18 Adeka Carpol SP-600 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
19 Adeka Carpol SC-800 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
20 Adeka Carpol T-400 Asahi Denka Co.，Ltd. Poly propylene oxide derivative
Comparative Examples 1
The polyamide matrix (ProductName: Macromelt (R) 6900 is by the Henkel preparation) and the carbon black of 100 weight portions of 50 weight portions are mixed in mixer.Further (80wt%/20wt%) mix prepares uniform mask material solution with normal butyl alcohol/toluene with this potpourri.Prepare the hectographic printing master with the method identical with embodiment 1, except with as the mask material solution of above-mentioned preparation form mask layer (C).
Use stamp infrared ray (non-ultraviolet ray) laser beam of the semiconductor laser of exporting from the 600mW energy under the 830nm wavelength, to shine the hectographic printing master, melt fully up to reaching mask layer.
Print with the hectographic printing version that makes in the Comparative Examples 1.As a result, remain on the photosensitive resin layer, thereby can not print character image clearly because melt fragment.
Industrial applicibility
As mentioned above, the present invention is characterised in that and uses the photosensitive lamination material as the letterpress master, described photosensitive lamination material has base material and lamination at least photosensitive resin layer and mask layer thereon, described photosensitive resin layer is light sensitivity to ultraviolet radiation, wherein mask layer has ultraviolet-absorbing and non-ultraviolet-absorbing concurrently, and the ultraviolet-absorbing of mask layer along with receiving non-ultraviolet radiation such as infrared ray or Ar radiation inactivation.
According to the present invention with aforementioned feature, the letterpress master can be provided, wherein can form the mask images layer with excellent contrast, and not make the photosensitive resin layer surface roughening of its bottom, and use this letterpress master to produce the method for relief printing plate.
Although described the present invention with reference to preferred embodiment, it should be understood that those skilled in the art can easily carry out various modifications and variations, and do not break away from spirit of the present invention. Accordingly, above-mentioned disclosure should only be interpreted as illustrative and should not be construed as limitation. The present invention is only limited by scope and all equal scope thereof of following claim.
List of references:
1. Jap.P. discloses 2916408
2. Japanese Patent Application Publication 2003-35954
3. Japanese Patent Application Publication 2003-35955
4. Japanese Patent Application Publication H11-153865
5. Japanese Patent Application Publication H9-166875
6. Japanese Patent Application Publication 2001-324815
7. Jap.P. discloses 2773981

Claims (15)

1. letterpress master comprises:
Base material;
Photosensitive layer, it is laminated on the described base material and is photosensitivity to ultraviolet radiation; And
Mask layer, it is laminated on the photosensitive layer, and described mask layer has the ability of ultraviolet radiation-absorbing and non-ultraviolet radiation, and the ultraviolet-absorbing of described mask layer is inactivation along with receiving described non-ultraviolet radiation.
2. according to the letterpress master of claim 1, wherein said non-ultraviolet radiation is infrared radiation.
3. according to the letterpress master of claim 2, wherein when the emittance of described infrared radiation is in preset range, along with the inactivation that receives the described ultraviolet-absorbing of described infrared radiation takes place there not being mask layer to melt down.
4. according to the letterpress master of claim 2, wherein when the emittance of infrared radiation is higher than predetermined value, along with the inactivation that receives described infrared radiation ultraviolet-absorbing melts generation with mask layer.
5. according to the letterpress master of claim 1, wherein said non-ultraviolet radiation is that wavelength peak is at 450 light that arrive in the 700nm scope.
6. according to the letterpress master of claim 1, the oxygen permeability coefficient of wherein said mask layer is 1 * 10 -17To 9 * 10 -10
7. according to the letterpress master of claim 1, wherein said mask layer comprises binder resin, acid forming agent and ultraviolet light absorber, and the ability of described ultraviolet light absorber ultraviolet radiation-absorbing is along with contacting and inactivation with acid.
8. according to the letterpress master of claim 7, wherein said binder resin comprises and is selected from least a of cellulose derivative, polyalkylene oxide derivative and urethane derivative.
9. according to the letterpress master of claim 1, further be included in the cover layer on the described mask layer.
10. method that is used to produce relief printing plate comprises:
Provide have base material, photosensitive resin layer and lamination mask layer thereon that lamination has sensitivity to ultraviolet light thereon, described mask layer has the ability of ultraviolet radiation-absorbing and non-ultraviolet radiation, and the ultraviolet-absorbing of described mask layer is inactivation along with receiving described non-ultraviolet radiation;
Shine described mask layer according to the picture pattern that is used to print with described non-ultraviolet radiation, described mask is changed into have for the transparent mask images layer that is subjected to irradiation zone of described ultraviolet radiation;
Shine described photosensitive resin layer via described mask images layer with described ultraviolet radiation; And
With the described master of development liquid development, remove the described photosensitive resin layer segment in the also uncured thus ultraviolet unirradiated zone of described ultraviolet radiation irradiation of no use, be formed on the resin bed that has relief pattern on the described base material thus, obtain described relief printing plate.
11. according to the method for claim 10, wherein said mask layer has the infrared ray-absorbable of non-ultraviolet-absorbing as described, and the non-as described ultraviolet radiation of its radiation of medium infrared carries out, and is used for described mask layer is changed into described mask images layer.
12. method according to claim 11, wherein said infrared radiation comprises that the emittance with infrared radiation is controlled in the preset range, makes the inactivation of the ultraviolet-absorbing that causes by described infrared radiation in described mask layer take place there not being mask layer to melt down.
13. method according to claim 11, wherein said infrared radiation comprises that the emittance with infrared radiation is controlled to be and is higher than predetermined value, makes the inactivation of the ultraviolet-absorbing that causes by described infrared radiation in described mask layer with the generation of melting of described mask layer.
14. according to the method for claim 10, the oxygen permeability coefficient of wherein said mask layer is adjusted at 1 * 10 -17To 9 * 10 -10Scope.
15. according to the method for claim 10, wherein said mask layer is by comprising that the composition of binder resin, acid forming agent and ultraviolet light absorber is made at least, the ability of described ultraviolet light absorber ultraviolet radiation-absorbing is along with contacting and inactivation with acid.
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